TY - JOUR
T1 - Ruthenocene-Type Complexes of N-Fused Porphyrins
AU - Toganoh, Motoki
AU - Matsuo, Hideaki
AU - Sato, Ayumi
AU - Furuta, Hiroyuki
N1 - Funding Information:
The present work was supported by a Grant-in-Aid for Young Scientists (25870504) to M.T. and a grant for scientific research to H.F. from MEXT, Japan (25248039).
Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/6/6
Y1 - 2016/6/6
N2 - Ruthenocene-type hybrid complexes with N-fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N-fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X-ray crystallography. [Ru(NFp)Cp] is a common low-spin ruthenium(II) complex and shows strong aromaticity. The Ru-Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three-dimensional d-π conjugated system. The HOMO-LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N-fused porphyrin, in which the HOMO-LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.
AB - Ruthenocene-type hybrid complexes with N-fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N-fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X-ray crystallography. [Ru(NFp)Cp] is a common low-spin ruthenium(II) complex and shows strong aromaticity. The Ru-Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three-dimensional d-π conjugated system. The HOMO-LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N-fused porphyrin, in which the HOMO-LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.
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U2 - 10.1002/chem.201600813
DO - 10.1002/chem.201600813
M3 - Article
C2 - 27135204
AN - SCOPUS:84973149479
SN - 0947-6539
VL - 22
SP - 8316
EP - 8322
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 24
ER -